CN107735456B

CN107735456B - Latex products with polymers and polymer adducts as fast setting additives

Info

Publication number: CN107735456B
Application number: CN201680036874.XA
Authority: CN
Inventors: K-J·金; 胡蓉; M·C·考夫曼
Original assignee: Arkema Inc
Current assignee: Arkema Inc
Priority date: 2015-06-23
Filing date: 2016-06-16
Publication date: 2021-06-15
Anticipated expiration: 2036-06-16
Also published as: EP3313939A1; CN107735456A; US20180162997A1; EP3313939A4; WO2016209691A1; US10829591B2; CA2990404A1; CA2990404C; MX2017016918A

Abstract

A latex product composition comprising an anionically stabilized latex; at least one volatile base compound; and one or more water-soluble polymers or polymer adducts having a backbone with a plurality of amine functional groups and hydroxyl functional groups. These polymers or polymeric adducts may be addition products formed from at least one polyfunctional amine compound reacted with one or more polyfunctional epoxy compounds, one or more monofunctional epoxy compounds, or combinations thereof. The polymers or polymeric adducts are formed by an addition reaction of the amine compound with the one or more epoxy compounds, wherein there are 1.3 to 3.8 amine functional groups per epoxy functional group. The addition product may be present at about 0.1 to 15.0 wt% based on the weight of the particles present in the anionically stabilized latex, and the at least one volatile base compound is present at about 1.0 wt% to 10.0 wt% based on the weight of the particles present in the anionically stabilized latex.

Description

Latex products with polymers and polymer adducts as fast setting additives

Technical Field

The present disclosure relates generally to aqueous compositions for use as coatings, inks, adhesives, and the like, incorporating water-soluble fast-setting additives. More specifically, the present disclosure relates to aqueous compositions comprising a dispersion of latex particles mixed with a water-soluble polymer or polymer adduct.

Background

The statements in this section merely provide background information related to the present disclosure and may not constitute prior art.

Latex products are widely used in a variety of coatings, adhesives, and inks because they provide several benefits, including that they are easy to handle and do not contain any significant amount of Volatile Organic Compounds (VOCs). One specific example of such a latex product is an acrylic latex composition used in traffic marking paints. Due to the market demand for products exhibiting reduced set times, the coatings industry has widely adopted coacervation techniques for latex products. Within the scope of such coacervation techniques, the protonated polyfunctional amine destabilizes the anionically stabilized latex particles present in the latex product after the latex product is coated onto a substrate. However, in order to maintain the stability of the modified latex particles in the latex product prior to application (e.g., during storage), a volatile amine is added to the latex product in order to increase the pH to a level that prevents protonation of the polyfunctional amine. When the latex product is applied to a substrate, the volatile amine escapes or evaporates from the applied coating composition. The loss of volatile amine results in a decrease in the pH of the applied latex coating composition. The decrease in pH triggers the coagulation of the latex particles in the applied coating composition, which results in faster setting times.

Many polyfunctional amine compounds have been used as fast-setting additives for latex products. U.S. patent No. 5,804,627 discloses a storage stable, fast curing, aqueous coating containing an amount of anionically stabilized latex, a polyfunctional amine, and a volatile base sufficient to prevent protonation of the amine.

In another approach to achieving fast set times, manufacturers of latex products tend to add a fast evaporating solvent, such as methanol, to the latex product. However, when polyfunctional amines having high basicity are present, because of their tendency to coagulate anionically stabilized latex particles present in the latex product, the addition of rapidly evaporating methanol to the latex product often results in instability of the latex product prior to its use (e.g., upon storage). Thus, achieving rapid set and stability in the presence of methanol remains a challenge that latex product formulations can be widely used by the coating industry.

Summary of The Invention

The present invention generally provides a latex product composition comprising, consisting of, or consisting essentially of: an anionically stabilized latex, at least one volatile base compound, and one or more polymers or polymer adducts having a backbone comprising a plurality of amine functional groups and hydroxyl functional groups. The polymer or polymer adduct may be water soluble and have a number average molecular weight in the range of about 200 to about 1,000,000 daltons and a nitrogen atom percentage of 5% to about 35% inclusive.

According to one aspect of the present disclosure, the polymer or polymer adduct may be an addition product formed from at least one polyfunctional amine compound reacted with one or more polyfunctional epoxy compounds, one or more monofunctional epoxy compounds, or a combination thereof; wherein the amine compound and the one or more epoxy compounds provide from 1.3 to 3.8 amine functional groups per epoxy functional group. The multifunctional epoxy compound may include epoxides of unsaturated hydrocarbons and fatty acids/oils, epoxy ethers of multifunctional alcohols, or combinations thereof, and the monofunctional epoxy compound may include epoxy ethers of monofunctional alcohols, epoxy esters of monofunctional alcohols, or combinations thereof. The polyfunctional amine compound may be selected from the group consisting of: ethylenediamine, butanediamine, diethylenetriamine, hexamethylenetriamine, triethylenetetramine, polyoxyethyleneamine, 2-methylpentamethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 2-diaminocyclohexane, isophoronediamine, tetraethylenepentamine, 4' -methylene-bis-cyclohexylamine, bis (3-methyl-4-aminocyclohexyl) methane, 2-bis (3-methyl-4-aminocyclohexyl) propane, 2, 6-bis (aminomethyl) norbornane, cyclohexanediamine, 3, 4-diaminofuran, phenylenediamine, 2, 4-diaminotoluene, polyalkylene oxide diamine, polyethylene oxide, polyethylene, Polyalkylene oxide triamines, 2,6 diaminotoluene, and combinations thereof. When desired, the at least one polyfunctional amine compound may be Diethylenetriamine (DETA), and the one or more polyfunctional epoxy compounds and/or the monofunctional epoxy compound may be ethylene glycol diglycidyl ether (EGDGE), n-Butyl Glycidyl Ether (BGE), polypropylene glycol diglycidyl ether (PPGDGE), or polyethylene glycol diglycidyl ether (PEGDGE).

The polymers, polymer adducts, and/or addition products of the present disclosure can have, consist of, or consist essentially of formula (F-1):

wherein R is₄Is alkyl or

And R is₃Is hydrogen or alkyl, and R₂Is alkyl, and R₁Is H, alkyl hydroxide, alkyl ether hydroxide or

Wherein w, x, y and z are integers in the range between 1 and 20, between 0 and 10, between 1 and 10,000 and between 0 and 10,000, respectively.

According to another aspect of the present disclosure, a polymer, polymer adduct or addition product is dissolved in an aqueous medium to form an aqueous solution having a viscosity in the range of about 100 centipoise to about 100,000 centipoise and a pH value of about 8 to about 12 when the aqueous solution comprises 70 wt.% of the polymer, polymer adduct or addition product dispersed in the aqueous medium. Such aqueous solutions exhibit a viscosity change of less than about 30% and maintain a clear appearance when held at a temperature of 50 ℃ for 30 days.

The anionically stabilized latex may comprise, consist of, or consist essentially of: polymer particles dispersed in an aqueous medium having up to 10 wt% anionic surfactant based on the weight of the polymer particles. The polymer particles may be selected from one of the following groups: acrylic copolymers, styrene-acrylic copolymers, vinyl copolymers, and combinations or mixtures thereof.

In the latex product composition, the polymer, polymer adduct, or addition product may be present in an amount between about 0.1 wt% and 15.0 wt% based on the weight of the polymer particles present in the anionically stabilized latex, and the at least one volatile base compound is present in an amount between about 1.0 wt% and about 10.0 wt% based on the weight of the polymer particles present in the anionically stabilized latex. The at least one volatile base compound may be selected from the group consisting of: ammonia, trimethylamine, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, and mixtures or combinations thereof.

According to yet another aspect of the disclosure, the polymer, polymer adduct or addition product may be selected from

Wherein R is H, alkyl hydroxide, alkyl ether hydroxide or

The latex product composition of the present invention may be a field and/or factory applied coating. The latex product compositions of the present disclosure may be used as is or incorporated into a variety of products including, but not limited to, coatings, paints, adhesives, sealants, caulks or inks for use in, but not limited to, traffic signs, construction or decoration (used synonymously herein), decking, dry drop, Pressure Sensitive Adhesive (PSA), roofing, cement and primer applications, and the like. The time for a coating formed using the latex product composition to become tack-free or dry out is at least 25% faster than the time required for a similar latex composition without the polyamine additive to become tack-free or dry out.

Further areas of applicability will become apparent from the description provided herein. It should be understood that the description and specific examples are intended for purposes of illustration only and are not intended to limit the scope of the present disclosure.

Drawings

The drawings described herein are for illustration purposes only and are not intended to limit the scope of the present disclosure in any way.

FIG. 1A is a schematic illustration of a latex product composition prepared in accordance with the teachings of the present disclosure placed in a container for storage;

FIG. 1B is a schematic illustration of a quick-drying mechanism associated with the latex product composition of FIG. 1A after application to a substrate;

FIG. 2 is a schematic illustration of a reaction scheme for forming a polymer adduct in accordance with the teachings of the present disclosure; and is

Fig. 3 is a schematic of another reaction scheme for forming a polymer adduct in accordance with the teachings of the present disclosure.

Detailed Description

The following description is merely exemplary in nature and is in no way intended to limit the disclosure, its application, or uses. For example, latex products prepared and used in accordance with the teachings contained herein are described throughout this disclosure in conjunction with traffic sign paints in order to more fully illustrate the composition and use of the latex products. It is contemplated that such latex products are incorporated and used within the scope of the present disclosure as coatings in other applications or as inks, paints, adhesives, caulks, sealants, mastics, and the like. It should be understood that throughout the specification, corresponding reference numerals indicate like or corresponding parts and features.

Referring to fig. 1A, composition 1 of the latex product of the present disclosure generally comprises, consists of, or consists essentially of: an anionically stabilized latex 3, at least one volatile base compound 5, and one or more polymers or polymer adducts 10 a. The anionically stabilized latex 3 represents a stable emulsion of polymer particles 15 dispersed in an aqueous medium 20. The aqueous medium 20 may comprise water as a primary solvent or diluent, either alone or as a mixture with one or more co-solvents or co-solvents. The polymer or polymer adduct 10a represents a compound formed by a covalent bond from a combination of amine and epoxy reactants.

The amount of water in the anionically stabilized latex 3 may be between about 30 wt.% to about 70 wt.% based on the total weight of the anionically stabilized latex 3; alternatively, in a range between 40 wt% to about 60 wt%. One or more co-solvents may optionally be present in an amount between about 0 wt% to about 30 wt%, based on the total weight of the anionically stabilized latex; alternatively, an amount ranging between 5 wt.% to about 25 wt.% is incorporated into the latex. Co-solvents may include coalescing aids and fast-evaporating solvents, which may aid in film formation and/or fast-drying behavior exhibited by traffic marking paints and other latex coatings. Several examples of co-solvents include, but are not limited to, methanol, propylene and glycol ethers, propylene and ethylene glycol, and 2,2, 4-trimethyl-1, 3-pentanediol monoisobutyrate (e.g., methanol, propylene and ethylene glycol ethers)

Istman Chemical Co., Ltd. (Eastman Chemical Co.)). Alternatively, the co-solvent is methanol (methyl alcohol) or methanol (methane).

The polymer particles 15 in the anionically stabilized latex 3 may be polymers or copolymers prepared from monomers including, but not limited to, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, styrene, butadiene, ethylene, vinyl acetate, vinyl versatate, vinyl chloride, acrylonitrile, acrylic acid, and methacrylic acid, and the like. The polymeric particles may also be derived from one or more ethylenically unsaturated acid monomers or their corresponding esters, including but not limited to acrylates and methacrylates. Alternatively, the polymeric particles include, but are not limited to, acrylic copolymers, styrene acrylic copolymers, vinyl copolymers, and mixtures or combinations thereof. The polymer particles may exhibit a glass transition temperature between about 0 ℃ and about 90 ℃.

The anionic charge on the polymer particles 15 may be obtained by any means known to those skilled in the art including, but not limited to, the inclusion of acid groups within or on the surface of the polymer particles. Several specific examples of such acid groups are acid groups derived from maleic acid, vinylsulfonic acid, acrylic acid, and methacrylic acid, to name a few. Negative charges can also be generated by using anionic surfactants and dispersants for dispersing the polymer particles into the aqueous medium. These surfactants or dispersants may include, but are not limited to, salts of fatty rosins and naphthenic acids, condensation products of sulfonic acids and formaldehyde, carboxylic acid polymers, alkyl sulfates, alkyl aryl sulfonates, and sulfosuccinates. The amount of anionic surfactant or dispersant used can range up to 10.0% by weight based on the weight of the polymer particles. Alternatively, the amount of surfactant used is greater than 0.1 wt% based on the weight of the polymer particles. When desired, the amount of anionic surfactant used is from about 0.5% to about 8.0% by weight based on the weight of the polymer particles; alternatively, between about 1.0 wt% and about 7.0 wt%. Additional details regarding anionically stabilized latexes are provided in U.S. patent No. 5,804,627 to f.landy (f.landy) et al, at 8.9.1998, which is incorporated herein by reference in its entirety. The latex composition may also contain one or more nonionic surfactants and/or cationic surfactants or dispersants, as well as other additives, as desired.

The volatile base compound 5 present in the latex product 1 raises the pH of the latex product 1 to a point equal to or above where substantially all of the amine functional groups present in the polymeric adduct 10a are in a non-ionic or non-protonated state. The volatile base compound 5 can include, but is not limited to, ammonia, trimethylamine, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, and mixtures or combinations thereof. Alternatively, the volatile base compound is ammonia. The amount of volatile base compound 5 to be added to the latex product 1 can be predetermined to be equal to or greater than the equivalent amount necessary to interact with each acidic functional group present in the polymer particles 15. Alternatively, the amount of volatile base compound 5 may be in the range of about 2 times to about 5 times greater than the equivalent amount necessary to interact with each acidic functional group present in the polymer particles 15. Alternatively, the amount of volatile base compound 5 present in the latex product ranges between about 1 and 10 weight percent based on the weight of the polymer particles 15 present in the anionically stabilized latex 3.

The polymer and polymer adduct 10a can have a polymer backbone comprising, consisting of, or consisting essentially of: a plurality of segments having amine functional groups and hydroxyl functional groups. The polymer and polymer adduct 10a generally comprises hydroxyl functional groups and/or alkylene ether and/or alkyl groups located between two adjacent amines present in the polymer backbone. A polymer backbone may be defined as a series of covalently bonded atoms that together create a molecular chain. The polymer and polymer adduct 10a can be formed as an addition product resulting from the reaction of a plurality of one or more functional amine compounds with one or more multifunctional epoxy compounds and/or one or more monofunctional epoxy compounds. Alternatively, the polymers and polymer adducts may be formed as addition products of at least one polyfunctional amine compound and a plurality of epoxy compounds; alternatively, three or more epoxy compounds are used. Polymers and polymeric adducts may be formed by reacting an amine compound with one or more epoxy compounds such that from 1.3 to 3.8 reactive amine functional groups are present per reactive epoxy functional group; alternatively, between 1.5 and 3.5 amine functional groups are present per epoxy functional group; alternatively, between 2.0 and 3.0 amine functional groups are present per epoxy functional group.

The polymer and polymer adduct 10a are water soluble. The polymer or polymer adduct 10a is present in the latex product 1 in an amount between about 0.1 and 15.0 weight percent based on the weight of the polymer particles 15 present in the anionically stabilized latex 3. Alternatively, the polymer or polymer adduct 10a may be present in the latex product 1 in an amount between about 0.5% and 5.0% by weight.

In the context of the present disclosure, the term "water-soluble" means that a homogeneous and transparent solution is formed when the polymer or polymer adduct is blended with water without the addition of any co-solvent. The term "clear solution" means that the solution transmits 90% or more of the illuminating visible light having a wavelength of 540 nm. The transmittance of visible light having a wavelength of 540nm can be measured by any conventional spectrophotometric method. The term "adduct" represents a compound formed by a combination of amine and epoxy reactants through a covalent bond. Aqueous solutions of polymers or polymer adducts formed in accordance with the teachings of the present disclosure exhibit sufficient stability. The term "sufficiently stable" or "sufficient stability" means that an aqueous solution of the polymer adduct exhibits a viscosity change of less than about 30% and retains a clear appearance when held at a temperature of 50 ℃ for 30 days. Viscosity is measured according to ASTM method D-2196 (American society for testing and materials, West Consheuchokan, Pa.).

The polymers and polymer adducts 10a prepared according to the teachings of the present disclosure provide flexibility in controlling the distance between amine functional groups. The degree of hydrophobicity exhibited by the polymer and polymer adduct 10a can be varied by varying the number of carbon atoms in the chain between adjacent amine groups in the polyfunctional amine compound and the number of alkyl and/or alkylene ether linkages between epoxide groups in the polyfunctional epoxy compound, the type of alkyl and/or alkylene ether linkages provided between epoxide groups in the polyfunctional epoxy compound, and the type of alkyl groups attached to the monoepoxy compound. Polymers and polymer adducts can thus be formed that can impart varying degrees of hydrophobicity when desired. This flexibility allows the structure of the polymer and polymer adduct 10a to be tailored to achieve methanol stability and desirable fast setting characteristics when incorporated into latex products by selecting the appropriate polyfunctional amine compound(s) and polyfunctional/monofunctional epoxy compound(s) to form the polymer and polymer adduct.

In addition, the number of alkyl and/or alkylene ether groups located between the epoxy groups present in the one or more polyfunctional epoxy compounds may also affect the degree of hydrophobicity associated with the polymer and the polymer adduct 10 a. Longer alkyl and/or alkylene ether linkages between epoxy groups may result in a more hydrophobic polymer and polymer adduct 10 a. In addition, the use of propylene ether linkages between the epoxy groups forms a polymer or polymer adduct 10a that is more hydrophobic than the use of ethylene ether linkages between the epoxy groups.

The epoxy compounds used to form the polymers and polymer adducts may include multifunctional epoxy compounds, monofunctional epoxy compounds, or combinations thereof. The polymers and polymer adducts also exhibit a number average molecular weight in the range of about 200 to about 1,000,000 uniform atomic mass units (amu) or daltons (Dalton) as measured by gel permeation chromatography; alternatively, between 200 and 500,000 daltons; alternatively, between 200 and 200,000 daltons. The polymer or polymer adduct may be collected or dissolved in water. These polymers or polymer adducts also contain a nitrogen atom percentage in the range of 5 to about 35%, wherein the nitrogen atom percentage (N)_Atom(s)%) was calculated according to equation (1):

wherein N is_AIs the number of nitrogen atoms per polyfunctional amine, M_AIs the molar amount of the polyfunctional amine, and W_RIs the total weight of the reactants. Alternatively, the nitrogen atomic percent of the polymer or polymer adduct is between about 10% and about 20%.

The polymer and polymer adduct may correspond to a formula defined below as (F-1), where w, x, y, and z are integers between 1 and 20, 0 and 10, 1 and 10,000, and 0 and 10,000, respectively. The integer y may alternatively be 10 to about 5000. The integer y can be from about 20 to about 1000, when desired.

Wherein R is₄Is alkyl or

These polymers and polymer adducts may contain from 1.3 to 3.8 amine functional groups per hydroxyl functional group. Alternatively, the polymers and polymer adducts may contain from 1.5 to 3.5 amine functional groups per hydroxyl functional group; alternatively, each hydroxyl functional group may contain from 2.0 to 3.0 amine functional groups.

In accordance with one aspect of the present disclosure, the polymer or polymer adduct may be mixed with the anionically stabilized latex by any means known to those skilled in the art including, but not limited to, milling, shaking, stirring, high shear mixing, planetary or other low shear mixing techniques, and combinations thereof. An aqueous solution of the polymer or polymer adduct is sufficiently stable and exhibits a viscosity in the range of about 100 centipoise to about 100,000 centipoise when the solution comprises about 70 weight percent of the polymer or polymer adduct dissolved in water. When desired, the viscosity is between about 100 centipoise to about 50,000 centipoise; alternatively, between 100 centipoise and 10,000 centipoise. The weight percent of the polymer adduct in aqueous solution can be measured according to ASTM test method D-1259 (American society for testing and materials, West Corschoenkan, Pennsylvania).

The aqueous solution also exhibits a pH of from about 8 to about 12; or from about 9 to about 11; or a pH of less than about 10.5. The pH of the blend of latex and polymer adduct was measured using a pH probe at 25 ℃. Further details regarding the Water-Soluble polymer Adducts of the present disclosure and Aqueous Solutions prepared therefrom are provided in co-pending U.S. provisional application No. 62/183304(IR 4257PSP) entitled "Water-Soluble Polymers and polymer Adducts and Aqueous Solutions Thereof (Water solvent Polymers and Polymeric additives aluminum With Aqueous Solutions Thereof) filed on 23.6.2015 by K-j. aurm, r. hu and j.l. gruff (K-j.kim, r.hu, and j.l.grove), which is incorporated herein by reference in its entirety.

When polymers and polymer adducts or aqueous solutions of these polymers or adducts are mixed with anionically stabilized latexes and at least one volatile base compound, the resulting latex products unexpectedly exhibit sufficient stability and excellent storage stability when formulated into paints. For example, a paint formulated with the latex product may exhibit a change in viscosity of less than about 10 Krebs Units (KU) when desired, when held at a temperature of 120 ° f for at least 7 days or when held at a temperature of 140 ° f for 7 days.

Further details regarding the Water-soluble polymer adducts of the present disclosure are provided in co-pending U.S. provisional application No. 62/183291(IR 4246PSP) entitled "Quick-Setting Coating Compositions with low pH Stability and Water Resistance" filed on 23.6.2015 at j.l. gruff, K-j. kim, r.hu, and w.devinforport, j.l. grove, K-j.kim, r.hu, and w.devinforport, which is incorporated herein by reference in its entirety.

The molecular weight of the polymer or polymer adduct may also affect the storage stability and fast setting characteristics of the latex product formed therefrom. The molecular weight of the polymers and polymer adducts of the present invention can be manipulated by appropriate selection of the number of amine functional groups present in the polyfunctional amine reactant, the number of epoxy groups present in the epoxy reactant, and/or the equivalent ratio of amine to epoxy functional groups present. Higher molecular weights can be obtained using polyfunctional amine reactants having a higher number of amine functional groups per molecule, epoxy reactants having a higher number of epoxy groups per molecule, or when the ratio of amine to epoxide is close to one (e.g., 1: 1).

The multifunctional epoxy compound that may be used to form the polymer or polymer adduct may comprise, consist of, or consist essentially of: epoxides of unsaturated hydrocarbons and fatty acids/oils, epoxy ethers of polyfunctional alcohols, or mixtures and combinations thereof. The epoxides of the unsaturated hydrocarbons and fatty acids/oils may include, but are not limited to, epoxides of vinylcyclohexene, dicyclopentadiene, cyclohexadiene, cyclododecadiene, cyclododecatriene, isoprene, 1, 6-hexadiene, butadiene, polybutadiene, divinylbenzene, castor oil, soybean oil, and mixtures or combinations thereof. Epoxy ethers of polyfunctional alcohols may include, but are not limited to, trimethylolpropane triglycidyl ether, pentaerythritol tetraglycidyl ether, trimethylolethane triglycidyl ether, ethylene glycol diglycidyl ether, sorbitol glycidyl ether, 2-methyl-1, 3-propanediol diglycidyl ether, neopentyl glycol diglycidyl ether, 2, 4-trimethylpentanediol diglycidyl ether, propylene glycol diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 1, 4-butanediol diglycidyl ether, 1, 6-hexanediol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and combinations thereof. Alternatively, the multifunctional epoxy compound may include ethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, or polyethylene glycol diglycidyl ether, and mixtures thereof.

The multifunctional epoxy compounds that may be used to form the polymeric adduct may comprise, consist of, or consist essentially of: epoxy ethers of monofunctional alcohols, epoxy esters of monofunctional alcohols, or mixtures and combinations thereof. Epoxy ethers of monofunctional alcohols may include, but are not limited to, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether, t-butyl glycidyl ether, n-pentyl glycidyl ether, isopentyl glycidyl ether, t-pentyl glycidyl ether, n-hexyl glycidyl ether, hexadecyl glycidyl ether, benzyl glycidyl ether, 2, 3-dimethoxybenzyl glycidyl ether, diacetone glycidyl ether, n-dodecyl glycidyl ether, 2-ethylhexyl glycidyl ether, and combinations thereof. Monofunctional epoxy esters of monofunctional alcohols may include, but are not limited to, glycidyl acetate, glycidyl pivalate, glycidyl 2-ethylhexanoate, glycidyl neodecanoate, and combinations thereof. Alternatively, the monofunctional epoxy compound may comprise n-butyl glycidyl ether, isobutyl glycidyl ether or tert-butyl glycidyl ether and mixtures thereof.

Polyfunctional amines that may be used to form the polymeric adduct may include, but are not limited to, ethylenediamine, butanediamine, diethylenetriamine, hexamethylenetriamine, triethylenetetramine, polyoxyethyleneamine, 2-methylpentamethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 2-diaminocyclohexane, isophoronediamine, tetraethylenepentamine, 4' -methylene-bis-cyclohexylamine, bis (3-methyl-4-aminocyclohexyl) methane, 2-bis (3-methyl-4-aminocyclohexyl) propane, 2, 6-bis (aminomethyl) norbornane, cyclohexanediamine, 3, 4-diaminofuran, poly (ethylene-co-ethylene-propylene-co-ethylene-diamine), poly (ethylene-co-ethylene-propylene-co-ethylene, Phenylenediamine, 2, 4-diaminotoluene, polyalkylene oxide diamine, polyalkylene oxide triamine, 2,6 diaminotoluene, and mixtures or combinations thereof. Alternatively, the polyfunctional amine may be diethylenetriamine, hexamethylenetriamine or triethylenetetramine and combinations thereof.

According to another aspect of the present disclosure, the amine compound or reactant is provided in a range of about 25 wt% to about 60 wt% relative to the combined weight of the amine and epoxy reactants, and the epoxy compound or reactant is provided in a range of about 40 wt% to about 75 wt% relative to the combined weight of the amine and epoxy reactants. Alternatively, the amine reactant is provided in a range of about 30 wt% to about 50 wt% relative to the combined weight of the amine and epoxy reactants, and the epoxy reactant is provided in a range of about 50 wt% to about 70 wt% relative to the combined weight of the amine and epoxy reactants.

When desired, as shown in the reaction scheme represented in fig. 2, the amine reactant can be Diethylenetriamine (DETA) and the epoxy reactant can be ethylene glycol diglycidyl ether (EGDGE), n-Butyl Glycidyl Ether (BGE), and polypropylene glycol diglycidyl ether (PPGDGE) or polyethylene glycol diglycidyl ether (PEGDGE). The resulting polymer and the polymer adduct formed therefrom may be represented by the formula (F-1A) or (F-1B).

Wherein R is H, alkyl hydroxide, alkyl ether hydroxide or

Table 1 below includes a non-exhaustive list of possible amine epoxide combinations that may be used to form the polymer adduct in accordance with the teachings of the present disclosure.

TABLE 1. several specific combinations of reactants for forming the Polymer Adduct (PA)

Reactants associated with the abbreviations used in table 1 include Diethylenetriamine (DETA), ethylene glycol diglycidyl ether (EGDGE), n-Butyl Glycidyl Ether (BGE), 2-ethylhexyl glycidyl ether (EHGE), polypropylene glycol diglycidyl ether (PPGDGE), and polyethylene glycol diglycidyl ether (peggdge).

The storage stability of latex products containing anionically stabilized latexes and polymer adducts depends to a large extent on the possibility of agglomeration between the two components in the aqueous phase. The basicity and molecular weight of the polymer or polymer adduct can be manipulated to prevent interaction with the polymer particles in the anionically stabilized latex during storage and to promote agglomeration with the polymer particles during the film forming stage during application. Referring now to fig. 1B, the latex product 1 is applied to a substrate by any means known to those skilled in the art including, but not limited to, roll coating, spray coating, spin coating, dip coating, brush coating, screen printing, ink jet application, and flow coating, to name a few. Spray coating includes airless spray, air spray, High Volume Low Pressure (HVLP) air spray, and air assisted airless spray, among others.

Once the latex product 1 is applied to a substrate, the aqueous medium 20 and the volatile base component 5 begin to evaporate and film 11 formation begins to occur. Evaporation of the volatile base component 5 results in a decrease in the pH of the latex product 1, which in turn causes the amine functional groups in the polymer or polymer adduct 10b to become positively charged (protonated). Evaporation of the aqueous medium 5 causes the positively charged polymer or polymer adduct 10b to interact with the negatively charged polymer particles 15, thereby promoting flocculation.

The latex composition may further comprise, consist of, or consist essentially of: one or more additional polymers, which may or may not be anionically stabilized, and any other known or desired additives. Additional polymers may include, but are not limited to, polymers or copolymers derived from one or more of (meth) acrylate, vinyl aromatic, ethylenically unsaturated aliphatic or vinyl ester monomers, and various combinations thereof. The formulated coating composition containing latex product 1 can be prepared by blending, mixing, etc. with other additives known to those skilled in the art. Other additives may include, but are not limited to, any type of pigment or colorant, filler, dispersant or surfactant, coalescent, pH neutralizer, plasticizer, defoamer, surfactant, thickener, biocide, co-solvent, rheology modifier, wetting or spreading agent, leveling agent, conductive additive, adhesion promoter, antiblocking agent, anti-cratering or anti-cracking agent, antifreeze, corrosion inhibitor, antistatic agent, flame retardant, optical brightener, UV absorber or other light stabilizer, chelating agent, crosslinker, leveler, flocculant, humectant, biocide, lubricant, odorant, oil, wax or anti-slip aid, antifouling or stain resist, and mixtures and combinations thereof. The selection of the additive to be incorporated into the coating composition is determined based on a variety of factors including the nature of the polymer or latex dispersion and the intended use of the coating composition, to name a few.

Several examples of pigments and colorants include, but are not limited to, metal oxides such as titanium dioxide, zinc oxide, or iron oxide, and organic dyes or combinations thereof. Examples of fillers may include, but are not limited to, calcium carbonate, nepheline syenite, feldspar, diatomaceous earth, talc, aluminosilicates, silica, alumina, clay, kaolin, mica, pyrophyllite, perlite, barite, or wollastonite, and combinations thereof.

Several examples of co-solvents and plasticizers include ethylene glycol, propylene glycol, diethylene glycol, combinations thereof, and the like. Typical coalescents that contribute to film formation during drying include, but are not limited to, ethylene glycol monomethyl ether, ethylene glycol monobutyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monobutyl ether, and diethylene glycol monoethyl ether acetate, and combinations thereof.

Several examples of dispersants may include, but are not limited to, any known nonionic surfactant, such as sulfosuccinates, higher fatty alcohol sulfates, aryl sulfonates, alkyl sulfonates, ammonium, alkali metal, alkaline earth metal, and lower alkyl quaternary ammonium salts of alkylaryl sulfonates, and/or ionic surfactants, such as alkyl phenoxy polyethoxy ethanol or ethylene oxide derivatives of long chain carboxylic acids, and polyacid dispersants, such as polyacrylic or polymethacrylic acids or salts thereof, and hydrophobic copolymeric dispersants, such as copolymers of acrylic, methacrylic, or maleic acid with hydrophobic monomers.

Several examples of thickeners may include, but are not limited to, hydrophobically modified ethylene oxide urethane (HEUR) polymers, hydrophobically modified alkali soluble emulsion (HASE) polymers, hydrophobically modified hydroxyethyl cellulose (HMHEC), hydrophobically modified polyacrylamides, and combinations thereof.

The incorporation of various defoamers, such as, for example, Polydimethylsiloxanes (PDMS) or polyether-modified polysiloxanes, can be performed to minimize foaming during mixing and/or application of the coating composition. Suitable biocides can be incorporated to inhibit the growth of bacteria and other microorganisms in the coating composition during storage.

Coatings that may include, but are not limited to, paints, adhesives, sealants, caulks, and inks formed from the latex compositions described herein, and methods of forming such coatings, are considered to be within the scope of the present disclosure. Generally, the coating is formed by applying the coating formulation described herein to a surface and allowing the coating to dry to form a coating or film. The resulting dried coating typically contains a minimum of the non-volatile components of the anionically stabilized latex and the polymers or polymer adducts of the present disclosure. The coating formulation and/or the dried coating may further comprise one or more additional polymers and/or additives as described above or known to those skilled in the art. The coating thickness may vary depending on the application of the coating. The thickness of the coating may be any thickness desired for a particular application; alternatively, the dry thickness of the coating ranges between about 0.025mm (1 mil) to about 2.5mm (100 mils).

The coating formulation can be applied to a variety of different surfaces including, but not limited to, metal, asphalt, concrete, stone, ceramic, wood, plastic, polymer, polyurethane foam, glass, and combinations thereof. The coating composition may be applied to the interior or exterior surfaces of a commercial product or article of manufacture or article. When desired, the surface may be an architectural surface, such as a roof, wall, floor, or a combination thereof.

According to one aspect of the present disclosure, each coating formulation can be formulated to meet the use requirements in specific application areas including, but not limited to, traffic paints, decorative or architectural, pressure sensitive adhesives, decking, "dry landing", roofing, cement, and primer applications, as further emphasized by the examples below. The coating formulation used in each of these applications may be formulated such that it comprises the latex product composition as described above or further defined herein, and optionally one or more additional polymers or other known or desired additives. The latex compositions used in these coating formulations generally include anionically stabilized latexes; at least one volatile base compound; and one or more polymers of formula (F-1); an addition product formed by reacting at least one polyfunctional amine compound with one or more polyfunctional and/or monofunctional epoxy compounds; or a polymeric adduct having a backbone consisting of a plurality of amine functional groups and hydroxyl functional groups.

Latex coating formulations formulated in accordance with the teachings of the present disclosure for traffic paint applications generally exhibit better stability at lower pH (e.g., pH in the range of 9-11), comparable drying (setting) times, and improved water resistance compared to conventional latex traffic paints comprising polyethyleneimine. The latex coating formulations of the present disclosure formulated for use in decorative or architectural applications also exhibit good stability at low pH values (pH in the range of 7 to 10), as well as better performance with respect to substrate adhesion and/or the amount of time required to become tack free or dry out, as compared to conventional latex coating formulations not containing the polymers and polymer adducts of the present invention. Similarly, latex coating formulations of the present disclosure used as pressure sensitive adhesives (pH in the range of 6 to 9), deck coatings (pH in the range of 7 to 9), or "dry drop" coating applications (pH in the range of 7 to 9) exhibit good stability, faster set properties, and enhanced water resistance and/or adhesion to substrates compared to conventional latex coating formulations that do not contain the polymers and polymer adducts of the present invention. In addition, other latex coating formulations prepared in accordance with the teachings of the present disclosure, including those coatings or paints formulated for roofing and primer applications as well as various sealants, caulks and inks, may exhibit similar characteristics or benefits over conventional latex formulations. Conventional latex compositions include those that do not contain any fast-drying additives ("as is"), as well as those that include conventional fast-drying additives such as Polyethyleneimine (PEI).

Aspects of the invention are described below:

1. a latex product composition comprising:

an anionically stabilized latex;

at least one volatile base compound; and

one or more polymers having the formula (F-1):

wherein R is₄Is alkyl or

And R is₃Is hydrogen or alkyl, and R₂Is alkyl, and R₁Is H, alkyl hydroxide or alkyl ether hydroxide or

2. In the latex product composition, these polymers contain from 1.3 to 3.8 amine functional groups per hydroxyl functional group;

wherein the polymers are water soluble and have a number average molecular weight in the range of about 200 to about 1,000,000 daltons.

3. In said latex product composition, the polymers are dissolved in water to form an aqueous solution having a viscosity in the range of about 100 centipoise to about 100,000 centipoise and a pH value of about 8 to about 12 when the aqueous solution comprises 70 wt.% of the polymers dissolved in the aqueous medium; the aqueous solution exhibits a viscosity change of less than about 30% and maintains a transparent appearance when held at a temperature of 50 ℃ for 30 days.

4. In said latex product composition, the anionically stabilized latex comprises polymer particles dispersed in an aqueous medium having up to 10 wt.% anionic surfactant, based on the weight of the polymer particles; the polymer particles are selected from one of the following groups: acrylic copolymers, styrene-acrylic copolymers, vinyl copolymers, and combinations or mixtures thereof;

wherein the polymers are present in an amount of between about 0.1 wt% and 15.0 wt% based on the weight of the polymer particles present in the anionically stabilized latex, and the at least one volatile base compound is present in an amount of between about 1.0 wt% and about 10.0 wt% based on the weight of the polymer particles present in the anionically stabilized latex, the at least one volatile base compound selected from the group consisting of: ammonia, trimethylamine, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, and mixtures or combinations thereof;

5. in the latex product composition, these polymers are selected from

Wherein R is H, alkyl hydroxide, alkyl ether hydroxide or

6. A latex product composition comprising:

an anionically stabilized latex;

at least one volatile base compound; and

an addition product of at least one polyfunctional amine compound reacted with one or more polyfunctional epoxy compounds, one or more monofunctional epoxy compounds, or a combination thereof;

wherein the amine compound and the one or more epoxy compounds provide from 1.3 to 3.8 amine functional groups per epoxy functional group;

wherein the addition product is water soluble, has a number average molecular weight in the range of about 200 to about 1,000,000 daltons, and comprises a nitrogen atom percentage of 5% to about 35%.

7. In the latex product composition, the polyfunctional epoxy compounds comprise epoxides of unsaturated hydrocarbons and fatty acids/oils, epoxy ethers of polyfunctional alcohols, or combinations thereof, and the monofunctional epoxy compounds comprise epoxy ethers of monofunctional alcohols, epoxy esters of monofunctional alcohols, or combinations thereof;

wherein the polyfunctional amine compounds are selected from the group consisting of: ethylenediamine, butanediamine, diethylenetriamine, hexamethylenetriamine, triethylenetetramine, polyoxyethyleneamine, 2-methylpentamethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 2-diaminocyclohexane, isophoronediamine, tetraethylenepentamine, 4' -methylene-bis-cyclohexylamine, bis (3-methyl-4-aminocyclohexyl) methane, 2-bis (3-methyl-4-aminocyclohexyl) propane, 2, 6-bis (aminomethyl) norbornane, cyclohexanediamine, 3, 4-diaminofuran, phenylenediamine, 2, 4-diaminotoluene, polyalkylene oxide diamine, polyethylene oxide, polyethylene, Polyalkylene oxide triamines, 2,6 diaminotoluene, and combinations thereof.

8. In the latex product composition, the at least one polyfunctional amine compound is Diethylenetriamine (DETA), and the plurality of polyfunctional epoxy compounds and/or monofunctional epoxy compounds are selected from the group consisting of: ethylene glycol diglycidyl ether (EGDGE), n-Butyl Glycidyl Ether (BGE), and polypropylene glycol diglycidyl ether (PPGDGE) and polyethylene glycol diglycidyl ether (PEGDGE).

9. In said latex product composition, the addition product is dissolved in water to form an aqueous solution having a viscosity in the range of about 100 centipoise to about 100,000 centipoise and a pH of about 8 to about 12 when the aqueous solution comprises 70 weight percent of the addition product; the aqueous solution exhibits a viscosity change of less than about 30% and maintains a transparent appearance when held at a temperature of 50 ℃ for 30 days.

10. In the latex product composition, the addition product has the formula (F-1):

wherein R is₄Is alkyl or

11. In said latex product composition, the anionically stabilized latex comprises polymer particles dispersed in an aqueous medium having up to 10 wt.% anionic surfactant, based on the weight of the polymer particles; these polymer particles are selected from the group consisting of: acrylic copolymers, styrene-acrylic copolymers, vinyl copolymers, and combinations or mixtures thereof.

Wherein the addition product is present in an amount of between about 0.1 wt% and 15.0 wt% based on the weight of the polymer particles present in the anionically stabilized latex, and the at least one volatile base compound is present in an amount of between about 1.0 wt% and about 10.0 wt% based on the weight of the polymer particles present in the anionically stabilized latex, the at least one volatile base compound selected from the group consisting of: ammonia, trimethylamine, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, and mixtures or combinations thereof;

12. in the latex product composition, the addition product is selected from

Wherein R is H, alkyl hydroxide, alkyl ether hydroxide or

13. A latex product composition comprising:

an anionically stabilized latex;

at least one volatile base compound; and

a polymeric adduct having a backbone comprising a plurality of amine functional groups and hydroxyl functional groups, the polymeric adduct having a number average molecular weight in the range of about 200 to about 1,000,000 daltons and comprising a nitrogen atom percentage of 5% to about 35%;

wherein the polymeric adduct is water soluble and is formed by reacting an amine compound with one or more epoxy compounds such that 1.3 to 3.8 reactive amine functional groups are present per reactive epoxy functional group.

14. In the latex product composition, the polymer adduct has the formula:

wherein R is₄Is alkyl or

15. In said latex product composition, the polymer adduct is dissolved in water to form an aqueous solution having a viscosity in the range of about 100 centipoise to about 100,000 centipoise and a pH of about 8 to about 12 when the aqueous solution comprises 70 weight percent of the addition product; the aqueous solution exhibits a viscosity change of less than about 30% and maintains a transparent appearance when held at a temperature of 50 ℃ for 30 days.

16. In said latex product composition, the anionically stabilized latex comprises polymer particles dispersed in an aqueous medium having up to 10 wt.% anionic surfactant, based on the weight of the polymer particles; these polymer particles are selected from the group consisting of: acrylic copolymers, styrene-acrylic copolymers, vinyl copolymers, and combinations or mixtures thereof;

wherein the polymer adduct is present in an amount of between about 0.1 wt% and 15.0 wt% based on the weight of the polymer particles present in the anionically stabilized latex, and the at least one volatile base compound is present in an amount of between about 1.0 wt% and about 10.0 wt% based on the weight of the polymer particles present in the anionically stabilized latex, the at least one volatile base compound being selected from one of the following groups: ammonia, trimethylamine, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, and mixtures or combinations thereof;

17. in the latex product composition, the polymer adduct is selected from

Wherein R is H, alkyl hydroxide, alkyl ether hydroxide or

18. The use of the latex product composition in coatings, paints, adhesives, sealants, caulks or inks.

19. A coating formulation for traffic paint applications comprising said latex product composition.

20. A coating formulation for decorative or architectural applications comprising said latex product composition.

21. A coating formulation for use as a pressure sensitive adhesive comprising said latex product composition.

22. A coating formulation for decking applications comprising the latex product composition.

23. A coating formulation for "dry drop" applications comprising said latex product composition.

24. A coating formulation for cementitious coating applications comprising said latex product composition.

25. The coating formulation further comprises one or more additives selected from the group consisting of: additional polymers, pigments or colorants, fillers, dispersants or surfactants, coalescents, pH neutralizers, plasticizers, defoamers, thickeners, biocides, co-solvents, rheology modifiers, wetting or spreading agents, leveling agents, conductivity additives, adhesion promoters, antiblocking agents, anti-cratering or anti-cracking agents, antifreeze agents, corrosion inhibitors, antistatic agents, flame retardants, optical brighteners, UV absorbers or other light stabilizers, chelating agents, crosslinking agents, leveling agents, flocculants, humectants, biocides, lubricants, odorants, oils, waxes or anti-slip aids, antifouling agents, and stain resists.

26. The coating formulation, when applied to a substrate, becomes tack-free or dries out at least 25% faster than the time required for a similar latex composition not containing these polymers to become tack-free or dry out.

The following specific examples are given to illustrate the polymer or polymer adduct and latex product compositions of the present disclosure, as well as the latex coating formulations formed therefrom and methods of making the same, and should not be construed as limiting the scope of the present disclosure. Those of skill in the art should, in light of the present disclosure, appreciate that many changes can be made in the specific embodiments which are disclosed and still obtain a like or similar result without departing from the spirit and scope of the disclosure. It will be further understood by those of skill in the art that any of the properties reported herein represent conventionally measured properties and can be obtained by a variety of different methods. The methods described herein indicate that such methods and others can be used without departing from the scope of the disclosure.

EXAMPLE 1 preparation of Polymer or Polymer adduct

This example illustrates the formation of a polymer or polymer adduct according to the reaction scheme shown in figure 2. Specifically, the formation of the polymer adduct (PA-5) as described in table 1 is used as an example to illustrate the formation of the polymer or polymer adduct. A total of 60 parts of Diethylenetriamine (DETA) were charged to a reaction vessel equipped with a nitrogen blanket. A total of 24 parts of ethylene glycol diglycidyl ether (EGDGE), 72 parts of n-Butyl Glycidyl Ether (BGE), and 14 parts of polypropylene glycol diglycidyl ether having a number average molecular weight of 640 (PEGDGE) were mixed in a beaker and transferred to an addition funnel. The reaction vessel temperature was raised to 80 ℃ with gentle stirring. The contents of the addition funnel were gradually added to the stirred reaction vessel over 1 hour while maintaining the temperature of the reaction vessel below 110 ℃. After the addition of the mixture of EGDGE, BGE and PEGDGE was complete, the reaction vessel was kept at 80 ℃ for 2.5 hours. Then 73 parts of deionized water were charged to the reaction vessel and mixed thoroughly to form an aqueous solution. The resulting aqueous solution exhibited a pH of 10.5 and a viscosity of 400 centipoise (at 25 ℃) and was found to be sufficiently stable.

Example 2 methanol stability test

A total of 10 grams of methanol was added to 50 grams of a mixture containing the latex and either conventional polyamine additives (e.g., polyethyleneimine) or the polymer and/or polymer adduct (PA-5) prepared in example 1 above. Conventional polyamines or polymers and/or polymer adducts are blended with the latex at 1 wt.% based on polymer solids. After about 1 minute of rapid stirring, the blended material was poured into a 190 micron filter. After the blended material passed through the filter, any material that did not pass through the filter was collected and weighed. % non-filterability was calculated based on 50 grams of the blended material. A lower% non-filterability means that the blend material exhibits better methanol stability, e.g., forms less non-filterable solids. As shown in table 2, the polymers or polymer adducts of the present disclosure clearly provide greatly improved methanol stability compared to conventional polyamine additives, even at lower pH values. Methanol stability is desirable for traffic sign applications in order to achieve coating stability, as methanol is widely used for fast setting properties.

TABLE 2 comparison of methanol stability between polyethyleneimine and polymer or polymer adduct of the present invention.

Example 3 comparison of white traffic paint formulations

White paints were prepared according to the formulation shown in table 3. The latex used in this example included an acrylic emulsion (X31215) and a styrene acrylic copolymer emulsion (X41191). First, component (A) was prepared under mild agitation at about 400 rpm. In this example, a polymer adduct (PA-5) or Polyethyleneimine (PEI) was incorporated into the latex for comparative purposes. Ammonia was added to achieve a pH of about 10.0. Then under mild stirring, defoaming agent, dispersing agent and TiO are added₂A pigment and a thickener (component (B)) are added to component (A). After mixing for 5 to 10 minutes, calcium carbonate and an antifoaming agent (component (C)) were added under high-speed stirring at about 2000 rpm. After 5 to 10 minutes of mixing, the stirring rate was reduced to about 400rpm, and then component (D) was added.

The test results for white paints, as shown in tables 3-5 and discussed further below, demonstrate that the polymers or polymer adducts of the present invention are effective and useful additives that enhance the drying time and water resistance of latex-based paints while maintaining excellent paint stability during storage prior to application. The drying time is measured according to ASTM standard test method D711 (american society for testing and materials, west cornescharken, state pennsylvania) at a relative humidity of 50% to 52%. A steel cylinder weighing 11 pounds of 14 ounces (5385 grams) was rolled along the dry traffic paint that had been applied to the glass plate. The paint is considered dry when no paint adheres to the O-ring surrounding the steel cylinder.

Table 3. formulation for preparing quick setting paint.

Water resistance was tested as follows. The paint was applied to the glass plate at a thickness of about 15 mils. After drying for 3 days at ambient conditions, the glass plates were immersed in water for 18 hours. After drying for 2 hours at ambient conditions, the paint film was visually inspected. The paint was considered to have failed when the film separated from the glass plate and/or air bubbles formed therein.

As shown in table 4, the addition of polyethyleneimine as a fast-setting additive to an acrylic or styrene-acrylic latex resulted in solidification of the paint during exposure to elevated temperatures of 120 ° f and 140 ° f. This clearly demonstrates that the addition of polyethyleneimine as a conventional fast drying (fast setting) additive to emulsion products is not a practical way to enhance the drying (setting) time of paints, as the paints become solid and unusable during storage prior to use. In contrast, the addition of the polymer or polymer adduct of the present invention to an acrylic or styrene-acrylic latex results in a paint that is very stable even after exposure to 120F for 2 weeks and 140F for 1 week.

Table 4 comparison of paint stability between polyethyleneimine and a polymer or polymer adduct of the present disclosure when blended with an emulsion product at 1.0 wt% based on polymer solids.

Before thermal exposure

After 7 days of thermal exposure at 120 ℃ F

After 14 days of thermal exposure at 120 ℃ F

After 7 days of heat exposure at 140 ° F

The results shown in table 5 demonstrate that the polymers or polymer adducts of the present disclosure when blended as additives with latex provide latex-based paints with faster drying (set) times and improved water resistance.

Table 5. drying time and water resistance of the polymers or polymer adducts of the present disclosure when blended with the emulsion product at 1.0 wt.% based on polymer solids.

Measured by ASTM Standard D-711

Example 4-Overall test method for comparing other latex coating formulations

The performance of coating formulations incorporating the polymers or polymer adducts of the present disclosure into anionically stabilized latexes can be compared to conventional coating formulations that do not contain additives that impart fast drying properties. Additionally, the performance can be evaluated by comparing the compositions of the present disclosure with coating formulations containing the same anionically stabilized latex in the presence of another quick drying polyamine compound, Polyethyleneimine (PEI). Only after the pH of the latex has been increased to 10 or higher by the addition of a volatile base compound (e.g., ammonia, etc.), does Polyethyleneimine (PEI) be added to the anionically stabilized latex in order to maintain the immediate and long term storage of the resulting latex coating formulation.

Stability at Low pHThe relative stability of a latex coating formulation comprising a polymer or polymer adduct of the present disclosure may be combined with the inclusion of another type of fast drying additiveComparative latex paint formulations. The latex is first adjusted to a predetermined pH value using aqueous ammonia. Subsequently, the polymer or polymeric amine-epoxy adduct of the present disclosure was added to the pH adjusted latex at 2.0 wt% based on total latex solids content to form a latex paint formulation. A separate comparative latex paint formulation was similarly prepared by adding Polyethyleneimine (PEI) at 2.0 wt.% to a quantity of pH-adjusted latex. The resulting latex coating formulation is considered stable when it is substantially free of grit and substantially free flowing. Failure occurs when the latex paint formulation coagulates and cannot be stirred. The above procedure is repeated using the latex adjusted to a lower predetermined pH value until the lowest pH limit is determined to maintain the stability of the resulting latex paint formulation.

Quick setting propertyThe drying time of the latex paint formulation can be compared by: the latex is first adjusted to a pH of 10.5 with aqueous ammonia and then 2 wt% based on total latex solids of the polymer or polymer adduct of the present disclosure or another fast drying additive PEI is added. Next, an 8 mil draw down of the coating composition resulted in the formation of a film, which was subsequently evaluated by touch according to ASTM D-1640 (American society for testing and materials, West Comschhekken, Pa.). As previously defined above, tack-free is still the time after the initial draw-off when the film is touched with a human finger without a tacky hand. Similarly, as previously defined above, the definition of dry out is still the time after the initial draw down when a slight pressure and bending is applied with a human finger, the membrane does not rupture.

Water resistance/adhesionThe water resistance and ability to maintain adhesion to a substrate of a film formed from a latex coating formulation comprising a polymer or polymer adduct of the present disclosure may be compared to conventional latex coating formulations that do not contain additives that impart quick drying properties. Additionally, the compositions of the present disclosure can be compared to coating formulations containing another quick-drying additive, PEI, and coating formulations without the quick-drying additive ("as is") to evaluate the same performance. As previously described above, the film was prepared by: blending with ammonia waterThe anionically stabilized latex was adjusted to a pH of 10.5 and then 2.0 wt.% of the polymer or polymer adduct of the present disclosure or PEI as a comparative additive was added based on the total solids content of the latex. The resulting latex coating formulation was then coated onto a glass substrate using an 8 mil draw down technique as previously described above. The film was dried at room temperature for 24 hours. The coated substrate was immersed in water for an additional 24 hours before visual inspection. The film that passes visual inspection retains adhesion to the glass surface and cannot be easily removed from the glass substrate, whereas the film that fails visual inspection has a large loss of adhesion to the glass surface.

The use of the polymers or polymer adducts of the present disclosure in latex coating, paint, adhesive, sealant, caulk or ink formulations is either the same as conventional latex formulations or enhances one or more of the stability at low pH, fast setting properties and water resistance/adhesion characteristics of such latex compositions. Conventional latex formulations include those compositions that do not contain any quick-drying additives ("as is"), as well as those compositions that include conventional quick-drying additives such as Polyethyleneimine (PEI).

In the following examples, latex coating formulations comprising a polymer or polymer adduct of the present disclosure formed from DETA, EGDGE, BGE, and PPGDGE reactants (see PA-1, table 1) are compared to similar latex coating formulations that do not contain a quick-drying additive and latex coating formulations that comprise Polyethyleneimine (PEI) as a quick-drying additive and latex coating formulations that do not contain a quick-drying additive ("as is"). The polymer or polymer adduct (PA-1) used in the examples below exhibited a viscosity of about 400 centipoise and contained about 14 atomic percent nitrogen, with about 2 amine functional groups present per epoxy functional group used for production.

Example 5 comparison of latex coatings for architectural or decorative applications

The stability, quick set performance, and water resistance/adhesion at low pH of various acrylic latex coating formulations containing the polymers or polymer adducts of the present disclosure, measured according to example 4, are compared in table 6 with the results obtained for similar latex formulations containing PEI or no fast-drying additive ("as is").

TABLE 6 stability at low pH, quick set, and Water/adhesion resistance results for architectural or decorative latex coatings

Emulsion L-1 ═

626-acrylic acid emulsion (Akema company)

Emulsion L-2 ═

636-acrylic acid emulsion (Akema company)

Emulsion L-3 ═

631-acrylic emulsion (Acoma corporation)

Emulsion L-4 ═

6413 vinyl acrylic copolymer emulsion (Akema company)

In all cases, latex coating compositions containing the polymer adducts of the present disclosure exhibit better pH stability than latex coating formulations containing PEI, a polyamine that can be used to impart quick drying to conventional latex compositions. Thus, for a given latex formulation (L-1 to L-4) containing the polymer adduct of the present disclosure, stability can be achieved at a lower pH than a comparable latex formulation containing PEI as a fast drying additive. Thus, when the polymers or polymer adducts of the present disclosure are incorporated into latex coating formulations, it is desirable to add a smaller amount of volatile base (e.g., ammonia, trimethylamine, triethylamine, etc.) to the coating formulation in order to achieve long-term stability.

It was found that the time for the latex coating formulations (L-1 to L-4) containing the polymer adducts of the present disclosure to become tack free and dry out was less than a similar latex coating formulation ("as is") without any fast drying additives. In addition, latex coating formulations containing the polymer adducts of the present disclosure exhibit non-stick and dry-out characteristics similar to latex coating formulations containing PEI as a fast-drying additive.

When latex coating formulations (L-1 to L-4) comprising the polymer adducts of the present disclosure are cast as films on glass panels, the resulting films exhibit greater adhesion to glass substrates when exposed to water than comparable latex coating formulations without the polymer adduct ("as is"). This example clearly demonstrates that the novel compositions of the present disclosure provide useful architectural and decorative coatings having fast setting and/or water resistance properties at low pH values below about 9.0.

Example 6 comparison of latex compositions for use as pressure sensitive Adhesives

Various acrylic latex Pressure Sensitive Adhesive (PSA) compositions comprising the polymers or polymer adducts of the present disclosure were compared in table 7 with the results of measurements obtained for low pH stability, fast setting performance, and water/adhesion resistance measured according to example 4 with similar latex PSA formulations comprising PEI or without a fast-drying additive ("as is"). The only change in the test method of example 4 used to compare PSA compositions in this example was the addition of a total of 1.6 wt% of polymer adduct or PEI to the latex instead of 2.0 wt% as described in example 4.

Table 7 stability at low pH, quick set performance and water/adhesion resistance results for Pressure Sensitive Adhesives (PSAs).

No ammonia added

Emulsion L-5 ═

9043-acrylic acid emulsion (Akema company)

Emulsion L-6 ═

9466 acrylic copolymer emulsion (Akema company)

Emulsion L-7 ═

9285 emulsion of styrene acrylic acid copolymer (Akema company)

In general, latex PSA compositions containing the polymer adducts of the present disclosure exhibit better pH stability than latex PSA compositions containing PEI, a polyamine that can be used to impart quick drying to conventional latex compositions. Thus, for a given latex PSA composition (L-5 or L-6) containing a polymer adduct of the present disclosure, stability may be achieved at a lower pH than a comparable latex PSA composition containing PEI as a fast-drying additive. Thus, when the polymers or polymer adducts of the present disclosure are incorporated into latex PSA compositions, it is desirable to add smaller amounts of volatile base compounds (e.g., ammonia, trimethylamine, triethylamine, etc.) to the PSA composition in order to achieve long-term stability.

It was found that the latex PSA compositions (L-5 to L-7) containing the polymer adducts of the present disclosure became tack free for a time approximately equal to a similar latex PSA composition ("as is") without any fast-drying additives. In addition, the latex PSA compositions containing the polymer adducts of the present disclosure exhibit at least similar, if not longer, tack free and dry out characteristics as compared to latex PSA compositions containing PEI as a fast-drying additive.

When latex PSA compositions (L-5 to L-7) comprising the polymer adducts of the present disclosure are cast as films on glass plates, the resulting films exhibit at least the same, if not higher, adhesion to glass substrates when exposed to water as compared to comparable latex coating compositions that do not contain the polymer adduct ("as is") or that utilize PEI as a fast-drying additive. Latex compositions oriented for use in pressure sensitive adhesives typically have a glass transition temperature much lower than ambient temperature because of the long bonding times required. This example clearly demonstrates that the novel compositions of the present disclosure provide useful pressure sensitive adhesives with improved water resistance and feasible bonding times.

Example 7 comparison of latex coatings applied to Deck Or for "Dry drop" application

The stability, quick set performance, and water resistance/adhesion at low pH of various acrylic latex coating compositions comprising the polymers or polymer adducts of the present disclosure measured according to example 4 are compared in table 8 with the results obtained for similar latex formulations comprising PEI or without a fast drying additive ("as is"). Dry drop coatings represent latex coating formulations in which under moderate humidity (about 50% relative humidity) and temperature (about 25 ℃) conditions, any overspray that occurs during coating application dries to non-adherent dust over a predetermined distance (e.g., drops).

The polymer or polymer adduct used in this example includes PA-1 as previously described and PA-2 formed using DETA and EGDGE as reactants. The PA-2 polymer or polymer adduct is formulated to exhibit a higher viscosity, a higher atomic percent of nitrogen, and a higher ratio of amine to epoxy functional groups than the PA-1 polymer or polymer adduct. The PA-2 polymer or polymer adduct used in this example exhibited a viscosity of about 2,000 centipoise; an atomic percent of nitrogen of about 22%; and about 3.2 amine functional groups per epoxy functional group.

Latex coating formulations containing the polymer adducts of the present disclosure exhibit greater pH stability compared to latex coating compositions containing PEI. For example, for latex coating formulations containing the polymer adducts of the present disclosure (L-8), stability can be achieved at lower pH than comparable latex coating formulations containing PEI as a fast-drying additive. Thus, when the polymers or polymer adducts of the present disclosure are incorporated into latex coating formulations, it is desirable to add a smaller amount of volatile base compound (e.g., ammonia, trimethylamine, triethylamine, etc.) to the coating composition in order to achieve long-term stability.

Table 8 stability at low pH, quick set performance and water/adhesion resistance results for the deck or dry drop latex coatings.

Latex L-8 ═ X31215-acrylic emulsion (akoma corporation)

It was found that the time for the latex coating formulation (L-8) containing the polymer adduct of the present disclosure (PA-1, PA-2) to become tack free and dry out was less than a similar latex coating formulation ("as is") without any fast drying additives. In addition, the latex coating formulation (L-8) containing the polymer adduct (PA-1) exhibited tack free and dry out characteristics similar to those of latex coating formulations containing PEI as a fast drying additive.

When a latex coating formulation (L-8) comprising the polymer adduct (PA-1, PA-2) of the present disclosure is cast into a film on a glass plate, the resulting film exhibits higher adhesion to a glass substrate when exposed to water than a comparable latex coating composition without the polymer adduct ("as is"), and similar adhesion to that exhibited by a latex composition comprising PEI as a fast-drying additive.

Example 8 comparison of latex coatings for use with Cement substrates

The stability and fast setting performance at low pH of an acrylic latex coating formulation comprising a polymer or polymer adduct of the present disclosure, measured according to example 4, is compared in table 9 with the results obtained for a similar latex formulation comprising PEI or no fast drying additive ("as is").

Latex coating formulations containing the polymer adducts of the present disclosure exhibit greater pH stability compared to latex coating compositions containing PEI. For example, for latex coating formulation L-1 containing the polymer adduct of the present disclosure, stability may be achieved at a lower pH than a comparable latex coating formulation containing PEI as a fast drying additive. Thus, when the polymers or polymer adducts of the present disclosure are incorporated into latex coating formulations, it is desirable to add a smaller amount of volatile base compound (e.g., ammonia, trimethylamine, triethylamine, etc.) to the coating composition in order to achieve long-term stability

It was found that the time for the latex coating formulation L-1 containing the polymer adduct of the present disclosure, PA-1, to become tack free and dry out was less than a similar latex coating formulation without any fast drying additives ("as is"). In addition, latex coating formulation L-1 containing polymer adduct (PA-1) exhibited tack free and dry out characteristics similar to those of latex coating formulations containing PEI as a fast drying additive.

TABLE 9 stability at Low pH and fast setting Performance results for Cement latex coatings

Emulsion L-1 ═

Acrylic emulsion (Akema Corp.)

In this specification, embodiments have been described in a manner that enables a clear and concise specification to be written, but it is intended and will be understood that the embodiments may be variously combined or separated without departing from the invention. For example, it will be understood that all of the preferred features described herein apply to all aspects of the invention described herein.

The foregoing description of the various forms of the invention has been presented for the purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise form disclosed. Many modifications or variations are possible in light of the above teaching. The form discussed was chosen and described to provide the best illustration of the principles of the invention and its practical application to thereby enable one of ordinary skill in the art to utilize the invention in various forms and with various modifications as are suited to the particular use contemplated. All such modifications and variations are within the scope of the invention as determined by the appended claims when interpreted in accordance with the breadth to which they are fairly, legally and equitably entitled.

Claims

1. A latex product composition comprising:

an anionically stabilized latex;

at least one volatile base compound; and

wherein the addition product is water soluble, has a number average molecular weight in the range of 200 to 1,000,000 daltons, and comprises a nitrogen atom percentage of 5% to 35%,

wherein the multifunctional epoxy compound is selected from the group consisting of: epoxides of unsaturated hydrocarbons, fatty acids, and fatty oils, epoxy ethers of polyfunctional alcohols, and combinations thereof, and the monofunctional epoxy compound is selected from the group consisting of: epoxy ethers of monofunctional alcohols, epoxy esters of monofunctional alcohols, and combinations thereof;

wherein the polyfunctional amine compound is selected from the group consisting of: ethylenediamine, butanediamine, diethylenetriamine, triethylenetetramine, polyoxyethyleneamine, 2-methylpentamethylenediamine, 1, 3-diaminopropane, 1, 5-diaminopentane, 1, 6-diaminohexane, isophoronediamine, tetraethylenepentamine, 4' -methylene-bis-cyclohexylamine, bis (3-methyl-4-aminocyclohexyl) methane, 2-bis (3-methyl-4-aminocyclohexyl) propane, 2, 6-bis (aminomethyl) norbornane, cyclohexanediamine, 3, 4-diaminofuran, phenylenediamine, 2, 4-diaminotoluene, polyalkylene oxide diamines, polyalkylene oxide triamines, 2, 6-diaminotoluene, and combinations thereof.

2. The latex product composition of claim 1, wherein the butanediamine is 1, 4-diaminobutane.

3. The latex product composition of claim 1, wherein the cyclohexanediamine is 1, 2-diaminocyclohexane.

4. The latex product composition according to claim 1, wherein the at least one polyfunctional amine compound is Diethylenetriamine (DETA) and the one or more polyfunctional epoxy compounds and/or monofunctional epoxy compounds are selected from the group consisting of: ethylene glycol diglycidyl ether (EGDGE), n-Butyl Glycidyl Ether (BGE), polypropylene glycol diglycidyl ether (PPGDGE), and polyethylene glycol diglycidyl ether (PEGDGE).

5. The latex product composition according to any one of claims 1-4, wherein the addition product is dissolved in water to form an aqueous solution having a viscosity in the range of 100 centipoise to 100,000 centipoise and a pH value of 8 to 12 when the aqueous solution comprises 70 wt.% of the addition product; the aqueous solution exhibits a change in viscosity of less than 30% and maintains a transparent appearance when held at a temperature of 50 ℃ for 30 days, wherein the viscosity is determined according to ASTM method D-2196 and the pH is measured at 25 ℃ using a pH probe.

6. The latex product composition according to any one of claims 1-4, wherein the addition product has the formula (F-1):

wherein R is₄Is alkylene or

And R is₃Is hydrogen or alkyl, and R₂Is alkylene, and R₁Is H, alkyl hydroxide, alkyl ether hydroxide or

7. The latex product composition according to claim 1, wherein the anionically stabilized latex comprises polymer particles dispersed in an aqueous medium having up to 10 wt.% of an anionic surfactant, based on the weight of the polymer particles;

wherein the polymer particles are selected from the group consisting of: acrylic copolymers, vinyl copolymers, and combinations thereof.

8. The latex product composition of claim 7, wherein the polymer particles are selected from the group consisting of: styrene-acrylic acid copolymers, vinyl-acrylic acid copolymers, and combinations thereof.

9. The latex product composition according to claim 1, wherein the addition product is present in an amount between 0.1 and 15.0 wt.% based on the weight of latex particles present in the anionically stabilized latex, and the at least one volatile base compound is present in an amount between 1.0 and 10.0 wt.% based on the weight of latex particles present in the anionically stabilized latex.

10. The latex product composition according to claim 1, wherein the at least one volatile base compound is selected from the group consisting of: ammonia, trimethylamine, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, and combinations thereof.

11. The latex product composition of claim 6, wherein the addition product is selected from

Wherein R is H, alkyl hydroxide, alkyl ether hydroxide or

12. A latex product composition comprising:

an anionically stabilized latex;

at least one volatile base compound; and

a polymeric adduct having a backbone comprising a plurality of amine functional groups and hydroxyl functional groups, the polymeric adduct having a number average molecular weight in the range of 200 to 1,000,000 daltons and comprising a nitrogen atom percentage of 5% to 35%;

wherein the polymeric adduct is water soluble and is formed by reacting one or more amine compounds with one or more epoxy compounds such that 1.3 to 3.8 reactive amine functional groups are present per reactive epoxy functional group,

wherein the polymeric adduct has the formula (F-1):

wherein R is₄Is alkylene or

13. The latex product composition according to claim 12, wherein the polymer adduct is dissolved in water to form an aqueous solution having a viscosity in a range of 100 centipoise to 100,000 centipoise and a pH value of 8 to 12 when the aqueous solution comprises 70 wt.% of the polymer adduct; the aqueous solution exhibits a change in viscosity of less than 30% and maintains a transparent appearance when held at a temperature of 50 ℃ for 30 days, wherein the viscosity is determined according to ASTM method D-2196 and the pH is measured at 25 ℃ using a pH probe.

14. The latex product composition according to claim 12, wherein the polymer adduct is present in an amount between 0.1 and 15.0 wt.% based on the weight of latex particles present in the anionically stabilized latex, and the at least one volatile base compound is present in an amount between 1.0 and 10.0 wt.% based on the weight of latex particles present in the anionically stabilized latex.

15. The latex product composition according to claim 12, wherein the anionically stabilized latex comprises polymer particles dispersed in an aqueous medium having up to 10 wt.% of an anionic surfactant, based on the weight of the polymer particles;

16. The latex product composition of claim 15, wherein the polymer particles are selected from the group consisting of: styrene-acrylic acid copolymers, vinyl-acrylic acid copolymers, and combinations thereof.

17. The latex product composition according to claim 12, wherein the at least one volatile base compound is selected from one of the following groups: ammonia, trimethylamine, triethylamine, dimethylethanolamine, morpholine, N-methylmorpholine, and combinations thereof.

18. The latex product composition according to claim 12, wherein the polymer adduct is selected from

Wherein R is H, alkyl hydroxide, alkyl ether hydroxide or

19. Use of the latex product composition according to claim 1 or 12 in coatings, adhesives, sealants, caulks or inks.

20. Use of the latex product composition according to claim 1 or 12 in paints.

21. A coating formulation for traffic paint applications, decorative applications, pressure sensitive adhesives, decking applications, "dry drop" applications, or cementitious coating applications, the coating formulation comprising the latex product composition of claim 1 or 12.

22. Use of a coating formulation comprising the latex product composition of claim 1 or 12 in traffic paint applications, decorative applications, pressure sensitive adhesives, decking applications, "dry drop" applications, or cementitious coating applications.

23. The coating formulation of claim 21, wherein the coating formulation is for traffic paint applications and when applied, the coating formulation becomes tack-free or dries out at least 25% faster than the time required for a latex composition that does not comprise the addition product of claim 1 or the polymer adduct of claim 12 to become tack-free or dry out.